Betaine esters of polyoxyalkylene ether

ABSTRACT

An emulsifying agent for emulsion polymerization comprising at least one compound selected from the group consisting of (i) betaine esters of polyoxyalkylene alkyl ethers, (ii) betaine esters of polyoxyalkylene alkylphenyl ethers, (iii) betaine esters of polyoxyalkylene dialkylphenyl ethers, (iv) betaine esters of polyoxyalkylene phenyl ethers having two or more benzene nuclei, and (v) betaine esters of polyoxyalkylene polyol ethers. This emulsifying agent is suitable for use in the emulsion polymerization of polymer emulsions capable of forming a film having an excellent water resistance, transparency, and smoothness.

This application is a continuation of Ser. No. 251,007 filed Sept. 27,1988, now abandoned which is a continuation of U.S. Ser. No. 869,781filed June 2, 1986, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to emulsifying agents for emulsionpolymerization. More specifically, it relates to emulsifying agentssuitable for use in the emulsion polymerization of polymer emulsionscapable of forming a film having an excellent water resistance,transparency, and smoothness.

2. Description of the Related Art

Various surfactants have been heretofore used as emulsifying agents inthe production of polymer emulsions from the emulsion polymerization ofunsaturated monomers. Of these surfactants, cationic surfactants such asalkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts,polyoxyethylene alkyl amine, polyoxyethylene alkyl trimethylene diamine,polyoxyethylene alkylmethyl ammonium salts, polyoxyethylene alkyldimethyl trimethylene ammonium salts,2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolium betaine,2-alkyl-N-carboxyethyl-N-hydroxyethyl imidazolium betaine, and N-alkyldimethyl amine oxide are widely used.

When the above-mentioned conventional emulsifying agents are used,however, a large amount of agglomerates are formed during thepolymerization and the particle sizes of the resultant polymer emulsionsbecome large. In addition, the mechanical stability, chemical stability,and storage stability of the resultant polymer emulsions are adverselyaffected due to the use of the conventional emulsifying agents.Furthermore, when the polymer emulsions are used as a coatingcomposition and an adhesive, the properties thereof are also affecteddue to the use of the conventional emulsifying agents.

On the other hand, it has been proposed in, for example, Angew. Chem.,71, 604 (1959) that decomposable glycine betaine alkyl esters be usedas a cationic surfactant to solve the above-mentioned problems. However,when the glycine betaine alkyl esters are used as an emulsifying agent,the film formed from the resultant polymer emulsion has a poor waterresistance, transparency, and smoothness.

SUMMARY OF THE INVENTION

Accordingly, the objects of the present invention are to eliminate theabove-mentioned problems of the conventional emulsifying agents and toprovide an emulsifying agent suitable for use in the emulsionpolymerization of polymer emulsions capable of forming a film having anexcellent water resistance, transparency, and smoothness.

Another object of the present invention is to provide an emulsifyingagent having reduced foaming properties and good antifoaming effects.

Other objects and advantages of the present invention will be apparentfrom the following description.

In accordance with the present invention, there is provided anemulsifying agent for emulsion polymerization comprising at least onecompound selected from the group consisting of (i) betaine esters ofpolyoxyalkylene alkyl ethers, (ii) betaine esters of polyoxyalkylenealkylphenyl ethers, (iii) betaine esters of polyoxyalkylenedialkylphenyl ethers, (iv) betaine esters of polyoxyalkylene phenylethers having two or more benzene nuclei, and (v) betaine esters ofpolyoxyalkylene polyol ethers.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The betaine esters usable in the present invention can be typicallyrepresented by the following general formulae (I) to (V).

(1) Betaine esters of polyoxyalkylene alkyl esters (i.e., AEB): ##STR1##wherein R₁ represents an alkyl or alkenyl group having 8 to 20 carbonatoms, R₂ represents an alkylene group having 2 to 4 carbon atoms, R₃represents an alkylene group having 1 to 5 carbon atoms, R₄ to R₆independently represent an alkyl group having 1 to 3 carbon atoms or--C₂ H₄ OH, n represents an average addition mole number of 1 to 20, andX represents an inorganic or organic anion.

(II) Betaine esters of polyoxyalkylene alkylphenyl ethers (i.e., APEB):##STR2## wherein R₂ represents an alkylene group having 2 to 4 carbonatoms, R₃ represents an alkylene group having 1 to 5 carbon atoms, R₄ toR₆ independently represents an alkyl group having 1 to 3 carbon atoms or--C₂ H₄ OH, R₇ represents an alkyl group having 6 to 20 carbon atoms, nrepresents an average addition mole number of 1 to 20, and X representsan inorganic or organic anion.

(III) Betaine esters of polyoxyalkylene dialkylphenyl ethers (i.e.,DAPEB): ##STR3## wherein R₁₁ and R₁₂ independently represent an alkylgroup having 6 to 20 carbon atoms, R₁₃ represents an alkylene grouphaving 2 to 4 carbon atoms, R₁₄ represents an alkylene group having 1 to5 carbon atoms, R₁₅, R₁₆, and R₁₇ independently represent an alkyl grouphaving 1 to 3 carbon atoms or --C₂ H₄ OH, l is an average addition molenumber of 1 to 30, and X is an inorganic or organic anion.

(IV) Betaine esters of polyoxyalkylene phenyl ethers having two or morebenzene nuclei (i.e., DBPEB): ##STR4## wherein R₁₃ represents analkylene group having 2 to 4 carbon atoms, R₁₄ represents an alkylenegroup having 1 to 5 carbon atoms, R₁₅, R₁₆, and R₁₇ independentlyrepresent an alkyl group having 1 to 3 carbon atoms or --C₂ H₄ OH, R₁₈represents a hydrogen atom or an alkyl group having 1 to 20 carbonatoms, l is an average addition mole number of 1 to 30, X is aninorganic or organic anion, and Y represents ##STR5##

wherein R₁₉ and R₂₀ represent a hydrogen atom or an alkyl group having 1to 20 carbon atoms, x is an integer of 1 to 5, and Z represents analkylene group having 3 to 8 carbon atoms, an oxygen group, a sulfurgroup, or a carbonyl group.

(V) Betaine ester of polyoxyalkylene polyol ethers (i.e., APOEB):##STR6## wherein Aalc represents a polyol residue having 8 to 20 carbonatoms and Bt₁ to Bt₅ independently represent a hydrogen atom, a hydroxylgroup, or ##STR7## wherein R₁₃ represents an alkylene group having 2 to4 carbon atoms, R represents an alkylene group having 1 to 5 carbonatoms, R₁₅, R₁₆, and R₁₇ independently represents an alkyl group having1 to 3 carbon atoms or --C₂ H₄ OH, l is an average addition mole numberof 1 to 30, and X represents an inorganic or organic anion.

In the above-mentioned general formulae (I) to (V), R₁ may be linear orbranched groups preferably having 10 to 18 carbon atoms, R₇ may belinear or branched groups preferably having 8 to 18 carbon atoms, R₁₁and R₁₂ may be linear or branched groups preferably having 8 to 18carbon atoms, R₁₈ may be linear or branched groups preferably having 1to 12 carbon atoms when R₁₈ is an alkyl group, and the alcohol residueAalc may be linear or branched groups preferably having 10 to 18 carbonatoms. In addition, the alkylene oxide units --R₂ O-- or --R₁₃ O-- maybe introduced into the higher aliphatic residues, the long-chainalkylphenol residues, the long-chain dialkylphenol residues, the phenolresidues having two to more benzene nuclei, and the polyol residues byaddition polymerizing one or more alkylene oxides such as ethyleneoxide, propylene oxide, and butylene oxide, preferably ethylene oxidethereto. When two or more alkylene oxides are addition polymerized, theaddition may be in either the form of the so-called random addition or ablock addition. The preferable average addition mole number of thealkylene oxide is 1 to 20, more preferably 3 to 15. Furthermore, X inthe above-mentioned general formulae (I) to (V) preferably representsinorganic anions such as halides (e.g., Cl⁻, Br⁻) and organic anionssuch as CH₃ COO⁻, OSO₃ CH₃ ⁻, and OSO₃ C₂ H₅ ⁻.

Examples of the betaine esters of polyoxyalkylene polyol estersaccording to the above-mentioned general formula (V) can be representedby the following general formula (V') ##STR8## wherein R₁₃, R₁₄, R₁₅,R₁₆, R₁₇, m, p, l, and X are the same as defined above.

The above-mentioned compounds AEB, APEB, DAPEB, DBPEB, and APDEB havingthe general formulae (I) to (V) may be prepared in various manners.

For example, when the compounds (I) and (II) are prepared, higheraliphatic alcohols (A) or long-chain alkylphenols (B) are used as astarting material.

    R.sub.1 OH                                                 (A) ##STR9## wherein R.sub.1 and R.sub.7 are the same as defined above. That is, an alkylene oxide is added to the staring material to form alkoxylates. The resultant alkoxylates are reacted with lower haloalkyl carboxylic acids to form the esters, followed by reacting with lower trialkyl amines such as trimethyl amine and triethyl amine. Thus, the desired compounds (I) and (II) can be obtained. The anion X⊖ of the resultant compounds may be optionally converted to organic anions by using, for example, ion-exchange methods.

Furthermore, when the compounds (III), (IV), and (V) can be prepared inthe same manner as in the case of the compounds by using, as startingmaterials, the following compounds (C), (D), and (E). ##STR10##

wherein R₁₁, R₁₂, R₁₈, Y, and Aalc are the same as defined above and yis an integer of 2 to 5.

Generally speaking, the emulsion polymerization process comprises threesteps; emulsification, polymerization, aging. When the emulsifyingagents according to the present invention are used in the emulsionpolymerization process, the unsaturated monomers and water can beemulsified to form microemulsification states because of the excellentemulsification properties of the present emulsifying agents.Furthermore, a portion of the betaine esters according to the presentinvention is decomposed during the polymerization and aging steps andthe resultant decomposed products cooperatively act as a cosurfactant.Thus, polymer emulsions having an excellent polymerization stability anda good water resistance, transparency, and smoothness can be obtained.

Furthermore, when the betaine esters according to the present invention(i.e., AEB, APEB, DAPEB, DBPEVM and APOEB) are used in combination withconventional cosurfactants, the above-mentioned cooperative effects canbe effectively and advantageously obtained. As a result, the particlesize of the polymer emulsion obtained therefrom can be further reduced.Examples of such cosurfactants are as follows: ##STR11## wherein R₂₁represents an alkyl or alkenyl group having 8 to 20 carbon atoms, R₂₂represents an alkylene group having 2 to 4 carbon atoms, R₂₃ representsan alkyl group having 6 to 20 carbon atoms, R₂₄ and R₂₅ independentlyrepresent an alkyl group having 6 to 20 carbon atoms, R₂₆ represents analkylene group having 2 to 4 carbon atoms, R₂₇ represents a hydrogenatom or an alkyl group having 1 to 20 carbon atoms, q is an averageaddition mole number of 1 to 20, r is an average addition mole number of1 to 30, m is an integer of 8 to 20, p is an integer of 2 to 5.

When the cosurfactants are used, the present emulsifying agents (a) andthe cosurfactants (b) are used in an amount of, preferably, (a)/(b)=99/1to 6/4, more preferably 98/2 to 65/35. The use of a too large amount ofthe cosurfactants tends to cause the unpreferable decrease in thecharacteristics of the films formed from the resultant polymeremulsions. When the cosurfactants (b) are used, the use of thecosurfactants having the structures similar to those of the alcohol orphenol portions of the emulsifying agents to be used is preferable. Thecosurfactants may be separately added to the emulsion polymerizationmixture. However, when the cosurfactants having the structures similarto the portion of the emulsifying agents (i.e., the starting compoundsof the emulsifying agents) are used, the betaine esters according to thepresent invention are prepared in such a manner that the startingcompounds (i.e., the cosurfactants) remain in the reaction mixture.Thus, the mixtures of the emulsifying agents and the cosurfactants canbe prepared in the production step of the emulsifying agents and themixtures can be directly used in the emulsion polymerization.

The emulsifying agents according to the present invention can providesufficient action as an emulsifying agent for the emulsionpolymerization even when used alone. However, nonionic surfactants andpolymer substances capable of functioning as a protective colloid forthe polymer emulsions can be optionally used in addition to the presentemulsifying agents.

Examples of such nonionic surfactants are polyoxyethylene alkyl amine,polyoxyethylene alkyltrimethylene diamine, polyoxyethylene fatty acidesters, and polyoxypropylene-polyoxyethylene glycol (i.e., Pluronic typesurfactants). Especially, polyoxyethylene type nonionic surfactantshaving an average addition mole number of ethylene oxide of 5 to 80,preferably 8 to 60, based on one active hydrogen atom.

Examples of the above-mentioned water-soluble polymer substances arepolyvinyl alcohol and hydroxyethyl cellulose. When used, the nonionicsurfactants and/or the water-soluble polymer substances are preferablyused, together with the betaine esters according to the presentinvention, in an amount of 0.05 to 1.0 parts by weight based on 1 partby weight of the betaine esters.

The emulsifying agents according to the present invention can be usedfor the emulsion polymerization of one or more of various unsaturatedmonomers. Examples of such monomers are aliphatic multi-unsaturatedhydrocarbons such as butadiene, isoprene, 1,3-pentadiene, chloroprene,cyclopentadiene, and hexadiene; halogenated products of the aliphaticmulti-unsaturated hydrocarbons; aromatic multi-unsaturated hydrocarbonssuch as divinylbenzene and diisopropylbenzene; diester compounds of(meth)acrylic acid or crotonic acid with diols such as ethylene glycol,diethylene glycol, polyethylene glycol, propylene glycol, dipropyleneglycol, polypropylene glycol, polyethylene glycol-polypropylene glycolblock copolymer, 1,3-butylene glycol, and hydrogenated bisphenol A;diether and divinyl ether compounds of the above-mentioned diols with(meth)allyl alcohol or chroton alcohol; polyester compounds of(meth)acrylic acid or chrotonic acid with polyols such as glycerol,trimethylol propane, and pentaerythritol; polyether compounds andpolyvinyl ether compounds of said polyols with (meth)allyl alcohol orcrotonyl alcohol; methyl salt compounds of metals such as magnesium andcalcium with (meth)acrylic acid or chrotonic acid; ester compounds andvinyl ester compounds of (meth)acrylic acid or chrotonic acid with(meth)allyl alcohol or chrotone alcohol; diester compounds and divinylester compounds of dibasic acids such as phthalic acid, isophthalicacid, terephthalic acid, oxalic acid, succinic acid, adipic acid, maleicacid, fumaric acid, and itaconic acid with (meth)allyl alcohol orcrotonyl alcohol; polyester compounds and polyvinyl ester compounds ofpolybasic acids such as trimellitic acid and pyromellitic acid with(meth)allyl alcohol or crotonyl alcohol; metal salt compounds of metalssuch as magnesium and calcium with vinyl sulfonic acid orstyrene-p-sulfonic acid; unsaturated monobasic acids such as(meth)acrylic acid and crotonic acid; unsaturated dibasic acids such asmaleic acid, fumaric acid, and itaconic acid; monoester compounds ofunsaturated dibasic acids with monoethers of diols such as ethyleneglycol, diethylene glycol, triethylene glycol, propylene glycol, andtripropylene glycol and lower monohydric alcohols such as methylalcohol, ethyl alcohol, and butyl alcohol; unsaturated alcohols such as(meth)allyl alcohol and crotonyl alcohol; vinyl ether compounds ofpolyols such as ethylene glycol, diethylene glycol, triethylene glycol,propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butyreneglycol, bisphenol A hydroxide, glycerol, trimethylol propane, andpentaerithritol; ether compounds of the polyols with (meth)allyl alcoholor crotoxyl alcohol; monoester compounds of the polyols with(meth)acrylic acid or crotonic acid; ester compounds of monoalcoholssuch as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol,2-ethylhexyl alcohol, dodecyl alcohol, stearyl alcohol, phenyl alcohol,and benzyl alcohol with (meth)acrylic acid or crotonic acid; diestercompounds of the monohydric alcohol with unsaturated dibasic acids suchas maleic acid, fumaric acid, itaconic acid, and citraconic acid; estercompounds of monoether compounds of diols such as ethylene glycol,diethylene alcohol, and triethylene glycol and monohydric alcohols suchas methyl alcohol ethyl alcohol, and butyl alcohol with (meth)acrylicacid or crotonic acid; diester compounds of the monoether compounds withthe unsaturated dibasic acids, olefin hydrocarbons such as ethylene,propylene, butylene, isobutylene, octene, isooctene, decene, anddodecene; aromatic vinyl compounds such as styrene, chlorostyrene,2-methylstyrene, vinyl toluene, vinyl xylene, and vinyl naphthalene;vinyl halides such as vinyl fluoride, vinyl chloride, and vinyl bromide;vinylidene halides such as vinylidene fluoride, vinylidene chloride, andvinylidene bromide; unsaturated cyan compounds such as(meth)acrylonitrile, croton nitrile, 2-cyanoethyl acrylate,2-chloroacrylonitrile, and vinylidene cyanide; vinyl ester compounds ofcarboxylic acids such as acetic acid, propionic acid, butyric acid,lauric acid, stearic acid, benzoic acid, p-tert-butylbenzoic acid, andhersatic acid; ester compounds of monocarboxylic acid with (meth)allylalcohol or crotonyl alcohol; vinyl ether compounds of monohydricalcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butylalcohol, 2-ethylhexyl alcohol, dodecyl alcohol, stearyl alcohol, phenylalcohol, and benzyl alcohol; ether compounds of the monohydric alcoholswith (meth)allyl alcohol or crotonyl alcohol; vinyl ether compounds ofmonoether compounds of aliphatic monohydric alcohols having 1 to 4carbon atoms with diols such as ethylene glycol, diethylene glycol,triethylene glycol, propylene glycol, dipropylene glycol, andtripropylene glycol; ether compounds of monoether compounds with(meth)allyl alcohol or crotonyl alcohol; unsaturated aldehydes such as(meth) acrolein and croton aldehydes; (meth)acrylates having an aminogroup such as diethylaminomethyl(meth)acrylate anddiethylaminoethyl(meth)acrylate and the quaternary salts thereofcationized with methyl chloride; unsaturated glycidyl esters such asglycidyl(meth)acrylate; glycidyl ether such as (meth)allyl glycidylether; unsaturated amides such as (meth)acrylamide,dimethyl(meth)acrylamide, and dimethylaminopropyl(meth)acrylamide, andthe quaternary salts thereof cationized with methyl chloride;unsaturated amide derivatives such as methylol (meth) acrylamide andalkyl ether compounds of these acrylamides having C₁ to C4 alkyl group.

When the above-mentioned unsaturated monomers are polymerized orcopolymerized by using the emulsifying agents according to the presentinvention, any polymerization initiators generating cationic or nonionicfree radicals can be used. Example of such initiators are inorganic andorganic salts of 2,2'-azobis (2-amidinopropane), hydrogen peroxide andthe combinations thereof with reducing agents, cumene hydroperoxide,tert-butyl hydroperoxide and the combinations thereof with reducingagents, as well as potassium persulfate and ammonium persulfate.

The emulsifying agents according to the present invention can be used inthe same manner as in the conventional emulsifying agents when emulsionpolymerizing the above-mentioned unsaturated monomers. For example, theunsaturated monomers are emulsified in an amount of 20% to 70% byweight, typically, in water in the presence of 0.1% to 10% by weight,based on the weight of the unsaturated monomer, of emulsifying agent,and the emulsion polymerization is then carried out by adding 0.1% to 2%by weight, based on the weight of the unsaturated monomer, ofpolymerization initiators. Furthermore, a p^(H) adjustor, apolymerization degree regulator, and other conventional additives can beused as in the conventional manner.

When the polymer obtained from the emulsion polymerization is recoveredfrom the resultant emulsion, any conventional method including, forexample, the addition of inorganic salt electrolytes, the addition ofcoagulants, and the addition of solvents which are not soluble inpolymer substances but are soluble in water, can be used. However, inthe preferred embodiment of the present invention, the polymers in theresultant polymer emulsions can be advantageously coagulated orrecovered from the polymer emulsions by adjusting the pH of the polymeremulsion systems to 6 or more or by irradiating the resultant polymeremulsions with ultrasonic waves. This is because, when the pH of thepolymer emulsion is adjusted to 6, preferably 7 to 12, more preferably 8to 11, or when the polymer emulsion is irradiated with ultrasonic waveshaving a frequency of 200 KHz or less, preferably 100 KHz or less, theester bond portions of the betaine esters according to the presentinvention are readily decomposed.

As mentioned above, the emulsifying agents for emulsion polymerizationaccording to the present invention have no disadvantages when comparedto the conventional cationic emulsifying agents. Furthermore, the filmsformed from the polymer emulsions obtained by the present emulsifyingagent exhibit a remarkably excellent water resistance, transparency, andsmoothness. Especially when the betaine esters of polyoxyalkylenedialkylphenyl ethers, the betaine esters of polyoxyalkylene phenylethers having two or more benzene nuclei, or the betaine esters ofpolyoxyalkylene polyol ethers are used, emulsions exhibiting low formingproperties and good antifoaming effects can be obtained. Furthermore,the emulsions obtained by the present emulsifying agents have a goodchemical stability, freezing stability, and storage stability.

Accordingly, the polymer emulsions obtained by using the presentemulsifying agents are suitable for utilization in conventionalapplications such as coating compositions or paints, especially bakingpaints, adhesives, tackifiers, and fiber and paper finish, as well asthe formation of electrically conductive film. Furthermore, when thepolymer emulsions obtained by using the present emulsifying agents areused in the anti-static treatment of, for example, fibers, wovenfabrics, non-woven fabrics, and molded products of synthetic resins,electrically conductive treatments of, for example, reprographic paperand statically recording paper, as well as molding additives formagnetic materials and fine ceramics, excellent effects, which are notconventionally exhibited, can be obtained.

Furthermore, the polymer emulsions obtained by using the presentemulsifying agents are advantageously used as binders of heat-sensitiverecording paper. Thus, the heat-sensitive recording paper having animproved water resistant heat-sensitive recording layer and an excellentsensitivity and good image quality can be provided.

EXAMPLES

The present invention now will be further illustrated by, but is by nomeans limited to, the following Examples and Comparative Examples,wherein all parts are by weight unless otherwise specified.

Example 1

A glass reaction vessel provided with a thermometer, an agitator, areflux condenser, and a dropping funnel was charged with 3 parts of anemulsifying agent listed in Table 1 and 110 parts of water. Theemulsifying agent was dissolved in the water and the system was replacedwith nitrogen. Further, 70 parts of ethyl acrylate and 30 parts ofmethyl methacrylate were mixed to separately prepare the unsaturatedmonomer mixture.

A 10 part amount of the unsaturated monomer mixture and 5 parts of a 5%aqueous 2,2'-azobis(amidinopropane)hydrochloride solution were added tothe reaction vessel and the polymerization was then started at atemperature of 60° C. Thereafter, the remaining 90 parts of theunsaturated monomer mixture was continuously dropwise added to thereaction vessel over 90 minutes. At this time, 5 parts of a 5% aqueous2,2'-azobis(amidinopropane)hydrochloride solution was added with a halfof the above amount of the unsaturated monomer mixture. After completingthe addition of the unsaturated monomer mixture, the polymerizationmixture was aged at a temperature of 60° C. for 90 minutes.

The polymer emulsion thus obtained was cast on a glass plate having asize of 6 cm×8 cm and was then air dried at room temperature to form apolymer film having a thickness of 0.2 mm. The characteristics of thefilm thus obtained were evaluated as follows.

(1) Water resistance: The polymer film after air drying was heated at atemperature of 160° C for 4 hours and the film was then fully immersedin water contained in a Petri dish at a temperature of 20° C. The timeinterval for which newspaper typed letters having a size of 8 pointscould not be read was determined. The results are shown in the unit ofhours.

(2) Transparency: The haze of the polymer film was determined by a hazemeter.

(3) Smoothness: The surface conditions of the polymer film was visuallyobserved and the results were evaluated according to the followingstandards.

◯. . . Smooth and glossy film

Δ. . . Film having slight wrinkles and crazing

x . . . Film having remarkable wrinkles and crazing

The results are shown in Table 1.

As is clear from the results shown in Table 1, when the emulsifyingagents according to the present invention are used, polymer films havingan excellent water resistance, transparency, and smoothness wereobtained when compared with the conventional emulsifying agents.

                                      TABLE 1                                     __________________________________________________________________________    Emulsifying agent                                                             Chloroglycine betaine ester of EO addi-                                                                          Film characteristics                       tion product of alcohol (or phenol)                                                                              Water                                      Sample                  Average EO addition                                                                      resistance                                 No. Alcohol (or phenol) mole No. (EO- p)                                                                         (hr) Transparency                                                                         Smoothness                     __________________________________________________________________________    1   C.sub.12-14 sec. alcohol                                                                          3          24   13     ◯                  2   C.sub.18 sec. alcohol                                                                             3          40    6     ◯                  3   C.sub.12 prim. alcohol                                                                            3          27   20     ◯                  4   C.sub.16-18 prim. alcohol                                                                         3          32   17     ◯                  5   Octyl phenol        3          60   11     ◯                  6   Dodecyl phenol      3          65    9     ◯                   7* Chloroglycine betaine lauryl ester                                                                            3   34     X                               8* Chloroglycine cetostearyl ester                                                                               7   62     Δ                         9* Polyoxyethylene lauryl ether (EO- p = 30)                                                                     8   37     Δ                        10* Polyoxyethylene octylphenyl ether                                                                             4   39     Δ                            (EO- p = 30)                                                              __________________________________________________________________________     *Comparative Example                                                     

Example 2

The polymer emulsions were prepared in the same manner as in Example 1,except that a mixture of (a) chloroglycine betaine ester of the ethyleneoxide (i.e. EO) addition products of alcohol or phenol and (b) the EOaddition products of alcohol or phenol listed in Table 2 in an amount of(a)/(b)=9/1 (weight ratio) was used as the emulsifying agent. Theemulsifying agents were prepared in such a manner that, when the betaineester (a) was prepared from the EO addition products (b), the EOaddition products (b) remained in the reaction mixture in theabove-mentioned ratio.

The particle sizes of the resultant polymer emulsions were determined bya Coulter counter (manufactured by Coulter Electronics Inc.). Theresults are shown in Table 2.

From the polymer emulsions obtained above, the polymer films were formedin the same manner as in Example 1 and the characteristics of thepolymer film were determined in the same manner as in Example 1. Theresults are shown in Table 2.

When the cosurfactant component (b), i.e., 3 mole EO addition product ofC₁₂₋₁₄ secondary alcohol, was not used in the sample No. 11 (i.e.,corresponding to the sample No. 1 of Example 1), the particle size ofthe polymer emulsion was 0.20 μm. As is clear from the results shown inTable 2, the use of the cosurfactant component (b) decreases theparticle size of the resultant polymer emulsion.

                                      TABLE 2                                     __________________________________________________________________________    Emulsifying agent              Film characteristics                               (b) EO addition product of alcohol                                                                 Particle                                                                            Water                                          Sample                                                                            (or phenol)          size  resistance                                     No. Alcohol (or Phenol)                                                                             EO- p                                                                            (μm)                                                                             (hr) Transparency                                                                         Smoothness                         __________________________________________________________________________    11  C.sub.12-14 sec. alcohol                                                                        3  0.08  27   14     ◯                      12  C.sub.18 two chain type prim. alcohol                                                           3  0.06  55    7     ◯                      13  C.sub.12 prim. alcohol                                                                          3  0.07  33   18     ◯                      14  C.sub.16-18 prim. alcohol                                                                       3  0.07  38   16     ◯                      15  Octylphenol       3  0.05  84    9     ◯                      16  Dodecylphenol     3  0.04  96    8     ◯                       17*                                                                              Stearyl trimethyl ammonium chloride                                                                Partial                                                                              3   45     X                                                           coagulation                                           18*                                                                              Polyoxyethylene lauryl ether                                                                       0.6    8   37     Δ                                (EO- p = 30)                                                               19*                                                                              Polyoxyethylene nonylphenyl ether                                                                  0.5    6   29     Δ                                (EO- p = 30)                                                               20*                                                                              Lauryl dimethylamine oxide                                                                         Partial                                                                              4   33     Δ                                                     coagulation                                          __________________________________________________________________________     *Comparative Example                                                     

Example 3

The emulsion polymerization was carried out in the same manner as inExample 1, except that the chloroglycine betaine esters ofpolyoxyethylene cetostearyl ethers having various average ethylene oxideaddition mole numbers (i.e., EOp) were used as the emulsifying agents.

Polymer films were formed from the polymer emulsions obtained above andthe characteristics of the resultant polymer films were evaluated in thesame manner as in Example 1. The results are shown in Table 3.

As shown in Table 3, the sample Nos. 4, 21, 22, and 23 according to thepresent invention gave good results when compared with the Comparativesample Nos. 8 and 24. As is clear from the results shown in Table 3, thesuitable EOp of the betaine esters is 1 to 20.

                  TABLE 3                                                         ______________________________________                                                    Film characteristics                                                    Emulsifying Water                                                       Sample                                                                              agent       resistance                                                  No.   (EO- p)     (hr)     Transparency                                                                            Smoothness                               ______________________________________                                         8*    0           7       62        Δ                                   4     3          32       16        ◯                            21     7          72       13        ◯                            22    12          53       11        ◯                            23    18          30       17        ◯                             24*  23           6       31        Δ                                  ______________________________________                                         *Comparative Example                                                     

Example 4

The emulsion polymerization of ethyl acrylate and methyl methacrylatewas carried out in the same manner as in Example 1, except that thecomponent (a) and the component (b) listed in Table 4 were used in theweight ratio of (a)/(b)=17/3. The emulsifying agents were prepared insuch a manner that, when the betaine esters of the component (a) wereprepared from the component (b) In the above-mentioned ratio in thereaction mixture, some of the component (b) remained as an unreactedcomponent.

The particle sizes of the polymer emulsions obtained above and thecharacteristics of the polymer films were evaluated in the same manneras mentioned in Example 1.

When the component (a) was used alone, as the emulsifying agent, withoutusing the component (b) in the sample No. 25, the particle size of thepolymer emulsion thus obtained was 0.18 μm. In Table 4, the sample Nos.28 and 32 are Comparative Examples.

The results are shown in Table 4.

                                      TABLE 4                                     __________________________________________________________________________    Emulsifying agent                                                                    ##STR12##                                                                                          ##STR13##                                                                              Particle                                                                           Film characteristics                Sample No.                                                                          R.sub.1                                                                           R.sub.2                                                                          R.sub.3                                                                          R.sub.4, R.sub.5, R.sub.6                                                           n  X R.sub.1                                                                           R.sub.2                                                                          n size (μm)                                                                       Water resistance                                                                       Transparency                                                                         Smoothness           __________________________________________________________________________    25    C.sub.12 H.sub.25                                                                 C.sub.2 H.sub.4                                                                  CH.sub.2                                                                         C.sub.2 H.sub.5                                                                      5 Br                                                                              C.sub.12 H.sub.25                                                                 C.sub.2 H.sub.4                                                                   5                                                                              0.05 49       12     ∘        26    C.sub.12 H.sub.25                                                                 C.sub.2 H.sub.4                                                                  CH.sub.2                                                                         C.sub.2 H.sub.5                                                                     12 Br                                                                              C.sub.12 H.sub.25                                                                 C.sub.2 H.sub.4                                                                  12                                                                              0.07 37       16     ∘        27    C.sub.12 H.sub.25                                                                 C.sub.2 H.sub.4                                                                  CH.sub.2                                                                         C.sub.2 H.sub.5                                                                     18 Br                                                                              C.sub.12 H.sub.25                                                                 C.sub.2 H.sub.4                                                                  18                                                                              0.08 28       17     ∘        28    C.sub.12 H.sub.25                                                                 C.sub.2 H.sub.4                                                                  CH.sub.2                                                                         C.sub.2 H.sub.5                                                                     22 Br                                                                              C.sub.12 H.sub.25                                                                 C.sub.2 H.sub.4                                                                  22                                                                              0.6  5        35     Δ              29    C.sub.18 H.sub.37                                                                 C.sub.2 H.sub.4                                                                  C.sub.2 H.sub.4                                                                  CH.sub.3                                                                             4 Cl                                                                              C.sub.18 H.sub.37                                                                 C.sub.2 H.sub.4                                                                   4                                                                              0.06 52       7      ∘        30    C.sub.18 H.sub.37                                                                 C.sub.2 H.sub.4                                                                  C.sub.2 H.sub.4                                                                  CH.sub.3                                                                            11 Cl                                                                              C.sub.18 H.sub.37                                                                 C.sub.2 H.sub.4                                                                  11                                                                              0.07 43       13     ∘        31    C.sub.18 H.sub.37                                                                 C.sub.2 H.sub.4                                                                  C.sub.2 H.sub.4                                                                  CH.sub.3                                                                            17 Cl                                                                              C.sub.18 H.sub.37                                                                 C.sub.2 H.sub.4                                                                  17                                                                              0.08 30       16     ∘        32    C.sub.18 H.sub.37                                                                 C.sub.2 H.sub.4                                                                  C.sub.2 H.sub.4                                                                  CH.sub.3                                                                            23 Cl                                                                              C.sub.18 H.sub.37                                                                 C.sub.2 H.sub.4                                                                  23                                                                              0.5  7        29     Δ              __________________________________________________________________________

Example 5

The reaction vessel used in Example 1 was charged with 4 parts of theemulsifying agent listed in Table 5 and 110 parts of water. Thus, theemulsifying agent was dissolved in the water.

Further, 50 parts of butyl acrylate and 50 parts of styrene were mixedto separately prepare the unsaturated monomer mixture.

A 10 part amount of the unsaturated monomer mixture and 5 parts of a 5%aqueous 2,2'-azobis(amidinopropane)hydrochloride solution were added tothe reaction vessel and the polymerization was then started at atemperature of 60° C. Thereafter, the remaining 90 parts of theunsaturated monomer mixture was continuously dropwise added to thereaction vessel over 90 minutes. At this time, 5 parts of a 5% aqueous2,2'-azobis(amidinopropane)hydrochloride solution was added with a halfof the above amount of the unsaturated monomer mixture. After completingthe addition of the unsaturated monomer mixture, the polymerizationmixture was aged at a temperature of 60° C. for 90 minutes.

The polymer film was formed from the polymer emulsion obtained above andthe characteristics of the polymer film were determined in the samemanner as in Example 1.

The results are shown in Table 5.

                                      TABLE 5                                     __________________________________________________________________________    Emulsifying agent                                                              ##STR14##                      Film characteristics                          Sample No.                                                                          R.sub.7                                                                           R.sub.2                                                                          R.sub.3                                                                          R.sub.4, R.sub.5, R.sub.6                                                           n  X     Water resistance                                                                       Transparency                                                                         Smoothness                     __________________________________________________________________________    33    C.sub.8 H.sub.17                                                                  C.sub.3 H.sub.6                                                                  CH.sub.2                                                                         CH.sub.5                                                                            2  Cl    80       12     ∘                  34    C.sub.8 H.sub.17                                                                  C.sub.2 H.sub.4                                                                  CH.sub.2                                                                         C.sub.2 H.sub.5                                                                     7  Br    77       10     ∘                  35    C.sub.9 H.sub.19                                                                  C.sub.3 H.sub.6                                                                  CH.sub.2                                                                         C.sub.2 H.sub.4 OH                                                                  3  Cl    55       9      ∘                  36    C.sub.9 H.sub.19                                                                  C.sub.2 H.sub.4                                                                  CH.sub.2                                                                         CH.sub.3                                                                            5  Br    71       9      ∘                  37        C.sub.4 H.sub.8                                                                  CH.sub.2                                                                         C.sub.2 H.sub.4 OH                                                                  2  Cl    57       8      ∘                  38    C.sub.9 H.sub.19                                                                  C.sub.3 H.sub.6                                                                  CH.sub.2                                                                         CH.sub.3                                                                            1  CH.sub.3 COO                                                                        66       11     ∘                            C.sub.2 H.sub.4                                                                           2                                                       39    C.sub.12 H.sub.25                                                                 C.sub.3 H.sub.6                                                                  CH.sub.2                                                                         C.sub.2 H.sub.4 OH                                                                  5  Cl    68       11     ∘                  40    C.sub.12 H.sub.25                                                                 C.sub.2 H.sub.4                                                                  CH.sub.2                                                                         CH.sub.3                                                                            10 Cl    70       8      ∘                  41    C.sub.12 H.sub.25                                                                 C.sub.2 H.sub.4                                                                  C.sub.2 H.sub.4                                                                  CH.sub.3                                                                            4  CH.sub.3 COO                                                                        73       9      ∘                  42    C.sub.12 H.sub.25                                                                 C.sub.2 H.sub.4                                                                  CH.sub.2                                                                         CH.sub.3                                                                            14 Cl    65       7      ∘                  43    C.sub.18 H.sub.37                                                                 C.sub.2 H.sub.4                                                                  CH.sub.2                                                                         CH.sub.3                                                                            18 Cl    75       7      ∘                  __________________________________________________________________________

Example 6

The polymer emulsion was obtained in the same manner as in Example 5,except that the reaction vessel was charged with 4 parts of theemulsifying agent comprising the components (a) and (b) listed in Table6.

The particle size of the polymer emulsion and the characteristics of thepolymer film were determined in the same manner as in Example 1. Theresults are shown in Table 6.

When only the component (a) was used, without the component (b), as theemulsifying agent in the sample No. 44 (i.e., corresponding to thesample No. 34 of Example 5), the particle size of the resultant polymeremulsion was 0.16 μm.

                                      TABLE 6                                     __________________________________________________________________________    Emulsifying agent                                                                  Component (a)                                                             Sample                                                                            ##STR15##                                                                                           ##STR16##        Particle                                                                           ##STR17##                    No. R.sub.7                                                                           R.sub.2                                                                          R.sub.4, R.sub.5, R.sub.6                                                           n  X     R.sub.7                                                                            R.sub.2                                                                           n   (a)/(b)                                                                           size (μm)                                                                       resistance                                                                         parency                                                                            ness                __________________________________________________________________________    44  C.sub.8 H.sub.17                                                                  C.sub.2 H.sub.4                                                                  CH.sub.3                                                                            5  Br    C.sub.8 H.sub.17                                                                   C.sub.2 H.sub.4                                                                   5   92/8                                                                              0.04 81    9   ∘       45  C.sub.8 H.sub.17                                                                  C.sub.3 H.sub.6                                                                  C.sub.2 H.sub.4 OH                                                                  1  Cl    C.sub.8 H.sub.17                                                                   C.sub.3 H.sub.6                                                                   1   70/30                                                                             0.03 83    8   ∘       46  C.sub.8 H.sub.17                                                                  C.sub.2 H.sub.4                                                                  C.sub.2 H.sub.5                                                                     10 CH.sub.3 COO                                                                        C.sub.8 H.sub.17                                                                   C.sub.2 H.sub.4                                                                   10  85/15                                                                             0.06 74   11   ∘       47  C.sub.12 H.sub.25                                                                 C.sub.2 H.sub.4                                                                  CH.sub.3                                                                            7  Cl    C.sub.12 H.sub.25                                                                  C.sub.2 H.sub.4                                                                   7   82/18                                                                             0.05 79   10   ∘       48  C.sub.12 H.sub.25                                                                 C.sub.4 H.sub.8                                                                  C.sub.2 H.sub.4 OH                                                                  1  CH.sub.3 COO                                                                        C.sub.12 H.sub.25                                                                  C.sub.4 H.sub.8                                                                   1   95/5                                                                              0.07 72   12   ∘       49  C.sub.18 H.sub.37                                                                 C.sub.2 H.sub.4                                                                  CH.sub.3                                                                            5  Cl    C.sub.18 H.sub.37                                                                  C.sub.2 H.sub.4                                                                   5   94/6                                                                              0.03 85    6   ∘       50  C.sub.18 H.sub.37                                                                 C.sub.3 H.sub.6                                                                  C.sub.2 H.sub.4 OH                                                                  3  Cl    C.sub.18 H.sub.37                                                                  C.sub.3 H.sub.6                                                                   3   77/23                                                                             0.08 69   12   ∘       51  C.sub.18 H.sub.37                                                                 C.sub.3 H.sub.6                                                                  CH.sub.3                                                                            1  Cl    C.sub.18 H.sub.37                                                                  C.sub. 3 H.sub.6                                                                  1   67/33                                                                             0.04 82    7   ∘               C.sub.2 H.sub.4                                                                        4             C.sub.2 H.sub.4                                                                   4                                          52  C.sub.18 H.sub.37                                                                 C.sub.2 H.sub.4                                                                  CH.sub.3                                                                            15 Br    C.sub.18 H.sub.37                                                                  C.sub.2 H.sub.4                                                                   15  81/19                                                                             0.06 73   12   ∘       __________________________________________________________________________

Example 7

The emulsion polymerization of ethyl acrylate and methyl methacrylatewas carried out in the same manner as in Example 1 by using, as anemulsifying agent, (a) chloroglycine betaine ester of polyoxyethylenenonylphenyl ether (EOp=2) and (b) polyoxyethylene nonylphenyl ether(EOp=2) in the weight ratio listed in Table 7.

The emulsifying agent was prepared in such a manner that, when thebetaine ester of the component (a) was prepared from the component (b),the component (b) remained, as the unreacted compound, in the weightratio listed in Table 7. In addition, the results obtained by using thecomponent (a) alone are shown as the sample No. 53 in Table 7.

                  TABLE 7                                                         ______________________________________                                        Emulsifying agent                                                                            Parti-  Film characteristics                                   Sam- Compo-   Compo-   cle   Water                                            ple  nent     nent     size  resis-                                                                              Trans- Smooth-                             No.  (a)      (b)      (μm)                                                                             tance parency                                                                              ness                                ______________________________________                                        53   100       0       0.17  23    18     ◯                       54   98        2       0.1   25    16     ◯                       55   90       10       0.08  53    10     ◯                       56   75       25       0.05  34     6     ◯                       57   65       35       0.09  29     6     ◯                       ______________________________________                                    

Example 8

A glass reaction vessel provided with a thermometer, an agitator, areflux condenser, and a dropping funnel was charged with 3 parts of anemulsifying agent listed in Table 8 and 110 parts of water. Theemulsifying agent was dissolved in the water and the system was replacedwith nitrogen. Further, 70 parts of ethyl acrylate and 30 parts ofmethyl methacrylate were mixed to separately prepare the unsaturatedmonomer mixture.

A 10 part amount of the unsaturated monomer mixture and 5 parts of a 5%aqueous 2,2'-azobis(amidinopropane)hydrochloride solution were added tothe reaction vessel and the polymerization was then started at atemperature of 60° C. Thereafter, the remaining 90 parts of theunsaturated monomer mixture was continuously dropwise added to thereaction vessel over 90 minutes. At this time, 5 parts of a 5% aqueous2,2'-azobis(amidinopropane)hydrochloride solution was added with a halfof the above amount of the unsaturated monomer mixture. After completingthe addition of the unsaturated monomer mixture, the polymerizationmixture was aged at a temperature of 60° C. for 90 minutes.

The polymer emulsion thus obtained was cast on a glass plate having asize of 6 cm×8 cm and was then air dried at room temperature to form apolymer film having a thickness of 0.2 mm. The characteristics of thefilm thus obtained were evaluated as follows.

(1) Water Resistance: see Example 1.

(2) Transparency: see Example 1.

(3) Smoothness: see Example 1.

(4) Foaming Properties: The polymer emulsion was diluted with water to asolid concentration of 10% by weight. A 30 ml amount of the dilutedemulsion was added to a large test tube having a diameter of 25 mm and aheight of 220 mm and the test tube was plugged with a stopper. The testtube was shaken in a vertical direction at 100 times per 30 seconds andthe height of the foam thus generated was measured in terms ofmilliliters (ml).

The results are shown in Table 8.

As is clear from the results shown in Table 8, when emulsifying agentsaccording to the present invention are used, the polymer films having anexcellent water resistance, transparency, and smoothness were obtainedwhen compared with the conventional emulsifying agents.

In addition, very little foaming of the polymer emulsions of the sampleNos. 58 to 63 obtained above during the polymerization was observed. Thefoaming properties are also shown in Table 8. The sample Nos. 58 to 65are Examples according to the present invention and the sample Nos. 66to 69 are Comparative Examples. As is clear from the results shown inTable 8, the emulsions had low foaming properties and good antifoamingeffects, in addition to the excellent water resistance, transparency,and smoothness of the polymer films formed from the polymer emulsions,when the emulsifying agents according to the present invention wereused.

                                      TABLE 8                                     __________________________________________________________________________    Emulsifying agent                                                              ##STR18##                                                                     ##STR19##                                                                     No.Sample                                                                         ##STR20##                   resistanceTransparencySmoothnessWaterFilm                                     characteristics    diately30 sec.2                                                              min.Imme-AfterAfterFoam                                                       ing properties             __________________________________________________________________________    58   R.sub.11, R.sub. 12 = Octyl                                                                        l = 3 62    13     ∘                                                                       42  20  4                  59   R.sub.11, R.sub.12 = Dodecyl                                                                       l = 3 60    10     ∘                                                                       47  22  6                  60   R.sub.11, R.sub.12 = Dodecyl                                                                       l = 6 56    6      ∘                                                                       52  25  9                  61   Y = Cumyl R.sub.18 = H                                                                             l = 3 48    13     ∘                                                                       41  16  3                  62   Y = C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 R.sub.18 = H                                                 l = 3 56    14     ∘                                                                       38  14  3                  63   C.sub.m H.sub.2m = C.sub.12 -C.sub.14 Alkylene P = 2                                               l = 3 34    11     ∘                                                                       45  21  7                  64   C.sub.m H.sub.2m = C.sub.12 -C.sub.14 Alkylene P = 2                                               l = 6 30    7      ∘                                                                       48  22  9                  65   C.sub.m H.sub.2m = C.sub.18 Alkylene P = 2                                                         l = 3 46    12     ∘                                                                       47  20  6                  66   C.sub.m H.sub.2m+1 = C.sub.12 -C.sub.14 sec. Alkylene P                                            l = 3 24    13     ∘                                                                       110 96  77                 67   C.sub.m H.sub.2m+1 = C.sub.18 sec. Alkylene P = 1                                                  l = 3 40    6      ∘                                                                       100 92  78                 68   R.sub.11 = Octyl R.sub.12 = H                                                                      l = 3 60    11     ∘                                                                       105 8   70                 69   R.sub.11 = Dodecyl R.sub.12 = H                                                                    l = 3 65    9      ∘                                                                       95  85  76                 __________________________________________________________________________     *Comparative Example                                                     

Example 9

The polymer emulsions were prepared in the same manner as in Example 8,except that a mixture of (a) chloroglycine betaine ester of the ethyleneoxide (i.e. EO) addition products of dialkyl phenol, cumyl phenol,aralkyl phenol, and alkane diol and (b) the EO addition products ofdialkyl phenol, cumyl phenol, aralkyl phenol, and alkane diol listed inTable 2 in an amount of (a)/(b)=9/1 (weight ratio) was used as theemulsifying agent. The emulsifying agents were prepared in such a mannerthat, when the betaine ester (a) was prepared from the EO additionproducts (b), the EO addition products (b) in the above-mentioned ratioremained in the reaction mixture as an unreacted component.

The particle sizes of the resultant polymer emulsions were determined bya Coulter counter (manufactured by Coulter Electronics Inc. Ltd.). Theresults are shown in Table 9.

From the polymer emulsions obtained above, polymer films were formed inthe same manner as in Example 8 and the characteristics and foamingproperties of the polymer films were determined in the same manner as inExample 8. The results are shown in Table 9.

When the cosurfactant component (b), (i.e., the alkoxylate) was not usedin the sample Nos. 70, 73, 74, and 75, the particle sizes of the polymeremulsion were 0.18, 0.21, 0.17, and 0.25 μm, respectively. As is clearfrom the results shown in Table 9, the use of the cosurfactant component(b) decreases the particle size of the resultant polymer emulsion.

Furthermore, it was visually observed that there was very little foamingduring the emulsion polymerization.

                                      TABLE 9                                     __________________________________________________________________________    Emulsifying agent                                                              ##STR21##                                                                     ##STR22##                                                                     No.Sample                                                                         ##STR23##                  (μm)sizeParticle                                                                resistanceparencynessWaterTrans-Smoot                                        h-Film Characteristics                                                                        diately30 sec.2                                                              min.Imme-AfterAfterFoam                                                       ing properties             __________________________________________________________________________    70   R.sub.11, R.sub.12 = Nonyl                                                                        l = 3 0.04 58   9    ∘                                                                      48  20  4                  71   R.sub.11, R.sub.12 = Nonyl                                                                        l = 6 0.07 43   6    ∘                                                                      58  22  7                  72   R.sub.11, R.sub.12 = Octadecyl                                                                    l = 3 0.05 67   8    ∘                                                                      41  16  8                  73   Y = Cumyl R.sub.18 = H                                                                            l = 6 0.10 45   10   ∘                                                                      47  19  11                 74   Y = H[CH(C.sub.6 H.sub.5)CH.sub.2] .sub.2 R.sub.18                                                l = 6 0.08 52   9    ∘                                                                      45  18  7                  75   C.sub.m H.sub.2m = C.sub.12 -C.sub.14 Alkylene P = 2                                              l = 3 0.09 33   10   ∘                                                                      40  17  5                  76   C.sub.m H.sub.2m = C.sub.18 Alkylene P = 2                                                        l = 3 0.06 45   11   ∘                                                                      43  21  5                  77   C.sub.m H.sub.2m = C.sub.18 Alkylene P = 2                                                        l = 6 0.08 37   7    ∘                                                                      52  24  12                 __________________________________________________________________________

Example 10

The emulsion polymerization of ethyl acrylate and methyl methacrylatewas carried out in the same manner as in Example 8, except that thechloroglycine betaine ester of polyoxyethylene dioctyl phenyl etherhaving various average ethylene oxide addition mole number (i.e., EOp)shown in Table 10 was used as the emulsifying agent.

The characteristics of the resultant polymer films and the foamingproperties were evaluated in the same manner as in Example 8. Theresults are shown in Table 10.

As shown in Table 10, the sample Nos. 58, 79, 80 and 81 according to thepresent invention gave good results when compared with the Comparativesample Nos. 78 and 82. As is clear from the results shown in Table 10,the suitable EOp of the betaine esters if 1 to 30.

                  TABLE 10                                                        ______________________________________                                        Emulsi-    Film characteristics                                                                            Foaming                                          fying      Water                 properties                                   Sample                                                                              agent    Resis-  Trans- Smooth-                                                                              Imme- After                              No.   (EO.sup.-- P)                                                                          tance   parency                                                                              ness   diately                                                                             30 sec.                            ______________________________________                                         78*   0       12      58     Δ                                                                              40    20                                 58     3       62      13     ◯                                                                        42    20                                 79     7       59      10     ◯                                                                        48    22                                 80    18       35      21     ◯                                                                        58    23                                 81    27       33      22     ◯                                                                        63    26                                  82*  33       12      25     ◯                                                                        74    52                                 ______________________________________                                         *Comparative Example                                                     

Example 11

The reaction vessel used in Example 8 was charged with 4 parts of theemulsifying agent listed in Table 5 and 110 parts of water. Thus, theemulsifying agent was dissolved in the water.

Further, 50 parts of butyl acrylate and 50 parts of styrene were mixedto separately prepare the unsaturated monomer mixture.

A 10 part amount of the unsaturated monomer mixture and 5 parts of a 5%aqueous 2,2'-azobis(amidinopropane)hydrochloride solution were added tothe reaction vessel and the polymerization was then started at atemperature of 60° C. Thereafter, the remaining 90 parts of theunsaturated monomer mixture was continuously dropwise added to thereaction vessel over 90 minutes. At this time, 5 parts of a 5% aqueous2,2'-azobis(amidinopropane)hydrochloride solution was added with a halfof the above amount of the unsaturated monomer mixture. After completingthe addition of the unsaturated monomer mixture, the polymerizationmixture was aged at a temperature of 60° C. for 90 minutes.

Polymer film was formed from the polymer emulsion obtained above and thecharacteristics and foaming properties of the polymer film weredetermined in the same manner as in Example 8.

The results are shown in Table 11.

                                      TABLE 11                                    __________________________________________________________________________        Emulsifying agent                                                          Sample                                                                            ##STR24##                    Film characteristics   Imme-Afterpropert                                                           iesFoaming             No. R.sub.11,                                                                         R.sub.12 R.sub.13 R.sub.14 R.sub.15,                                                   R.sub.16,                                                                        R.sub.17                                                                           l X     Water resistance                                                                       Transparency                                                                         Smoothness                                                                          diately                                                                           30                 __________________________________________________________________________                                                               sec.               83  C.sub.9 H.sub.19                                                                  C.sub.4 H.sub.8                                                                        CH.sub.2                                                                         C.sub.2 H.sub.4 OH                                                                 2 Cl    54       10     ∘                                                                       45  21                 84  C.sub.9 H.sub.19                                                                  C.sub.3 H.sub.6                                                                        CH.sub.2                                                                         CH.sub.3                                                                           1 CH.sub.3 COO                                                                        63       7      ∘                                                                       52  24                         C.sub.2 H.sub.4                                                                        CH.sub.2                                                                              4                                                    85  C.sub.12 H.sub.25                                                                 C.sub. 3 H.sub.6                                                                       CH.sub.2                                                                         C.sub.2 H.sub.4 OH                                                                 1 Cl    60       13     ∘                                                                       46  18                 86  C.sub.12 H.sub.25                                                                 C.sub.2 H.sub.4                                                                        CH.sub.2                                                                         CH.sub.3                                                                           3 Br    59       15     ∘                                                                       40  19                 87  C.sub.12 H.sub.25                                                                 C.sub.2 H.sub.4                                                                        C.sub.2 H.sub.4                                                                  CH.sub.3                                                                           5 CH.sub.3 COO                                                                        60       11     ∘                                                                       45  20                 88  C.sub.12 H.sub.25                                                                 C.sub.2 H.sub.4                                                                        CH.sub.2                                                                         CH.sub.3                                                                           7 Cl    53       7      ∘                                                                       55  24                 89  C.sub.18 H.sub.37                                                                 C.sub.2 H.sub.4                                                                        CH.sub.2                                                                         CH.sub.3                                                                           5 Cl    64       12     ∘                                                                       44  19                 __________________________________________________________________________

Example 12

The polymer emulsions were prepared by using the emulsifying agentslisted in Table 12 in the same manner as in Example 11.

The characteristics of the polymer films and the foaming properties weredetermined in the same manner as in Example 8. The results are shown inTable 12.

                                      TABLE 12                                    __________________________________________________________________________    Emulsifying agent                                                              ##STR25##                                                                                      Oxyalkylene                                                 Sample                                                                            Phenol having two or more                                                                   portion  Film characteristics  Foaming properties           No.  benzene nuclei                                                                             EO(.sup.-- P)                                                                      PO(.sup.-- P)                                                                     Water resistance                                                                       Transparency                                                                         Smoothness                                                                          Immediately                                                                          After 30              __________________________________________________________________________                                                            min.                  90  Y = C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 R.sub.18 = H                                          3    2   55       13     ∘                                                                       41     16                    91  Y = C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 R.sub.18 = H                                          5    0   50       12     ∘                                                                       43     18                    92  Y = C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 R.sub.18 = H                                          7    0   51       10     ∘                                                                       47     18                    93  Y = C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 R.sub.18 = H                                          7    3   48       8      ∘                                                                       48     16                    94  Y = Cumyl R.sub.18 = H                                                                      4    1   58       12     ∘                                                                       40     15                    95  Y = Cumyl R.sub.18 = H                                                                      3    2   60       14     ∘                                                                       39     15                    96  Y = Cumyl R.sub.18 = H                                                                      5    0   55       10     ∘                                                                       43     17                    97  Y = Cumyl R.sub.18 = H                                                                      5    2   53       8      ∘                                                                       46     19                    __________________________________________________________________________

Example 13

The emulsion polymerization of ethyl acrylate and methyl methacrylatewas carried out in the same manner as in Example 8.

The foaming properties of the polymer emulsions obtained above and thefilm characteristics were evaluated in the same manner as in Example 8.

The results are shown in Table 13.

                                      TABLE 13                                    __________________________________________________________________________       Emulsifying agent                                                           Sam- ple                                                                         ##STR26##               Film characteristics  Foaming properties          No.                                                                              m   P R.sub.3                                                                          l  R.sub.5, R.sub.6, R.sub.7                                                           X     Water resistance                                                                       Transparency                                                                         Smoothness                                                                          Immediately                                                                          After 30              __________________________________________________________________________                                                            sec.                   98                                                                              12-14                                                                             2 C.sub.2 H.sub.4                                                                  5  CH.sub.3                                                                            Cl    31       8      ∘                                                                       45     19                     99                                                                              12-14                                                                             2 C.sub.2 H.sub.4                                                                  4  C.sub.2 H.sub.4 OH                                                                  Br    33       9      ∘                                                                       47     21                    100                                                                              12-14                                                                             3 C.sub.3 H.sub.6                                                                  6  CH.sub.3                                                                            CH.sub.3 COO                                                                        37       11     ∘                                                                       48     16                    101                                                                              16-18                                                                             2 C.sub.3 H.sub.6                                                                  4  CH.sub.3                                                                            Cl    46       7      ∘                                                                       44     15                             C.sub.2 H.sub.4                                                                  6                                                                 102                                                                              16-18                                                                             3 C.sub.2 H.sub.4                                                                  3  C.sub.2 H.sub.5                                                                     Cl    35       16     ∘                                                                       36     12                    103                                                                              16-18                                                                             3 C.sub.3 H.sub.6                                                                  6  CH.sub.3                                                                            CH.sub.3 COO                                                                        34       8      ∘                                                                       47     18                             C.sub.2 H.sub.4                                                                  12                                                                __________________________________________________________________________

Example 14

An unsaturated monomer mixture of 45 parts of α-methylstyrene, 10 partsof acrylonitrile, and 45 parts of methyl methacrylate, 1.5 parts of2,2'-azobis(amidino)propane hydrochloride, 150 parts of water, and 3.0parts of the emulsifying agent listed in Table 14 were charged to areaction vessel and, after replacing the vessel with nitrogen, thereaction mixture was allowed to polymerize at a temperature of 70° C.for 5 hours.

The pH of the polymer emulsion obtained above was adjusted to a pH shownin Table 14 and the separation condition of the polymer from the waterwas evaluated visually and by the determination of the absorbance of theseparated water as follows:

◯. . . The polymer was completely separated from the water and theseparated water was crystal clear. The absorbance of the water was lessthan 0.5.

Δ. . . The polymer was insufficiently separated from the water and theseparated water was white and turbid. The absorbance of the water wasnot less than 0.5 but less than 1.0.

x . . . The polymer was not separated from the water and the absorbanceof the water was 1.0 or more.

The results are shown in Table 14.

As is clear from the results shown in Table 14, when the unsaturatedmonomers were emulsion polymerized in the presence of the betaine estertype emulsifying agents, followed by adjusting the pH of the resultantpolymer to 6 or more, the polymer compounds contained in the emulsionseffectively coagulated.

Furthermore, the aqueous phase was removed after coagulating the polymercompound according to the above-mentioned treatment, followed bycentrifugally separating the solid content. Thus, the solid content wasrecovered. In the case of the sample Nos. 104 to 109, the solid contentwas completely recovered.

                                      TABLE 14                                    __________________________________________________________________________     Emulsifying agent                                                             ##STR27##                       Separability of polymer Adjusted pH          Sample No.                                                                          R.sub.1                                                                           R.sub.2                                                                          R.sub.3                                                                          R.sub.4, R.sub.5, R.sub.6                                                           l m X.sup.⊖                                                                     3.0                                                                             5.3                                                                             7.7                                                                             10.0                                    __________________________________________________________________________    104   C.sub.12 H.sub.25                                                                 -- CH.sub.2                                                                         CH.sub.3                                                                            0 0 Cl    x x ∘                                                                   ∘                           105   C.sub.18 H.sub.37                                                                 -- CH.sub.2                                                                         C.sub.2 H.sub.5                                                                     0 0 Cl    x x ∘                                                                   ∘                           106   C.sub.18 H.sub.37                                                                 -- C.sub.2 H.sub.4                                                                  C.sub.2 H.sub.4 OH                                                                  0 0 CH.sub.3 COO                                                                        x x ∘                                                                   ∘                           107   C.sub.8 H.sub.17                                                                  C.sub.2 H.sub.4                                                                  CH.sub.2                                                                         CH.sub.3                                                                            1 3 Cl    x x ∘                                                                   ∘                           108   C.sub.8 H.sub.17                                                                  C.sub.3 H.sub.6                                                                  CH.sub.2                                                                         CH.sub.3                                                                            1 1 Cl    x x ∘                                                                   ∘                                     C.sub.2 H.sub.4                                                                             2                                                     109   C.sub.12 H.sub.25                                                                 C.sub.2 H.sub.4                                                                  CH.sub.2                                                                         CH.sub.3                                                                            1 5 Br    x x ∘                                                                   ∘                           110*.sup.1                                                                          Sodium alkylbenzene sulfonate                                                                           x x x x                                       111*.sup.1                                                                          Hydrogenated tallow fatty acid sodium salt                                                              x x x x                                       112*.sup.1                                                                          Polyoxyethylene nonylphenyl ether (- p = 9.7)                                                           x x x x                                       113*.sup.1                                                                          Trimethyl monostearyl ammonium chloride                                                                 *.sup.2                                                                         *.sup.2                                                                         *.sup.2                                                                         *.sup.2                                 __________________________________________________________________________     *.sup.1 Comparative Example                                                   *.sup.2 Emulsion polymerization impossible                               

Example 15

A 3 part amount of chloroglycine betaine esters of polyoxyethylene (p=3)octylphenyl ether, 150 parts of ester, 2.0 parts of2,2'-azobis(amidino)propane hydrochloride, and the unsaturated monomermixture listed in Table 15 were charged to the reaction vessel used inExample 14 and, after replacing the vessel with nitrogen, the reactionmixture was allowed to polymerize in the same manner as in Example 14.

The pH of the polymer emulsion obtained above was adjusted to 9 and theseparation condition of the polymer from the water was evaluated in thesame manner as in Example 14.

The results are shown in Table 15.

After the polymer compounds were coagulated by the above-mentionedtreatment, the solid was recovered in the same manner as in Example 14.In the case of the sample Nos. 114 to 118, the solid contents werecompletely recovered as in the case of the sample Nos. 104 to 109.

                  TABLE 15                                                        ______________________________________                                                                        Separ-                                        Sam- Unsaturated monomer        ability                                       ple  Kind                 Part      of                                        No.  A         B         C      (A/B/C) polymer                               ______________________________________                                        114* Polybu-   Styrene   Acrylo-                                                                              50/35/15                                                                              ◯                              tadiene             nitrile                                              115  Styrene   Acrylo-     --   71.5/28.5/0                                                                           ◯                                        nitrile                                                        116  α-Methyl-                                                                         Acrylo-     --   70/30/0 ◯                              styrene   nitrile                                                        117* Polybu-   Styrene   Methyl-                                                                              50/35/15                                                                              ◯                              tadiene             meth-                                                                         acrylate                                             118  Styrene   Butadiene   --   90/10/0 ◯                         ______________________________________                                         *Graft polymer used.                                                     

Example 16

An unsaturated monomer mixture of 45 parts of α-methylethyrene, 10 partsof acrylonitrile, and 45 parts of methyl methacrylate, 1.5 parts of2,2'-azobis(amidino)propane hydrochloride, 150 parts of water, and 3.0parts of an emulsifying agent listed in Table 16 were charged to areaction vessel and, after replacing the vessel with nitrogen, thereaction mixture was allowed to polymerize at a temperature of 70° C.for 5 hours.

The polymer emulsion obtained above was subjected to ultrasonicirradiation for 3 minutes under the conditions of 100 W and 45 kHz. Theseparation condition of the polymer compounds and water was evaluated inthe same manner as in Example 14. The results are shown in Table 16.

As is clear from the results shown in Table 16, when the unsaturatedmonomers were emulsion polymerized in the presence of the betaine estertype emulsifying agents, followed by ultrasonic irradiation, the polymercompounds contained in the emulsions effectively coagulated.

Furthermore, the aqueous phase was removed after coagulation from thepolymer compound according to the above-mentioned treatment, followed bycentrifugally separating the solid content. Thus, the solid content wasrecovered. In the case of the sample Nos. 119 to 124, the solid contentwas completely recovered.

                                      TABLE 16                                    __________________________________________________________________________    Emulsifying agent                                                              ##STR28##                                                                    Sample No.                                                                          R.sub.1                                                                           R.sub.2                                                                          R.sub.3                                                                          R.sub.4, R.sub.5, R.sub.6                                                           l m X.sup.⊖                                                                     Separability of polymer                       __________________________________________________________________________    119   C.sub.12 H.sub.25                                                                 -- CH.sub.2                                                                         CH.sub.3                                                                            0 0 Cl    ∘                                 120   C.sub.18 H.sub.37                                                                 -- CH.sub.2                                                                         CH.sub.3                                                                            0 0 Br    ∘                                 121   C.sub.18 H.sub.37                                                                 -- C.sub.2 H.sub.4                                                                  C.sub.2 H.sub.4 OH                                                                  0 0 CH.sub.3 COO                                                                        ∘                                 122   C.sub.8 H.sub.17                                                                  C.sub.2 H.sub.4                                                                  CH.sub.2                                                                         CH.sub.3                                                                            1 3 Cl    ∘                                 123   C.sub.8 H.sub.17                                                                  C.sub.3 H.sub.6                                                                  CH.sub.2                                                                         CH.sub.3                                                                            1 1 Cl    ∘                                           C.sub.2 H.sub.4                                                                             2                                                     124   C.sub.12 H.sub.25                                                                 C.sub.5 H.sub.4                                                                  CH.sub.2                                                                         CH.sub.3                                                                            1 5 Br    ∘                                 125*.sup.1                                                                          Sodium alkylbenzene sulfonate                                                                           x                                             126*.sup.1                                                                          Polyoxyethylene lauryl ether sulfate (.sup.-- P = 3)                                                    x                                             127*.sup.1                                                                          Hydrogenated tallow fatty acid sodium salt                                                              x                                             128*.sup.1                                                                          Polyoxyethylene nonylphenyl ether (- p = 9.7)                                                           x                                             __________________________________________________________________________     *.sup.1 Comparative Example                                              

Example 17

A 3 part amount of chloroglycine betaine esters of polyoxyethylene (p=3)stearyl ether, 150 parts of water, 2.0 parts of2,2'-azobis(amidino)propane hydrochloride, and the unsaturated monomermixture listed in Table 17 were charged to the reaction vessel used inExample 14 and, after replacing the vessel with nitrogen, the reactionmixture was allowed to polymerize in the same manner as in Example 14.

The resultant polymer emulsion was subjected to ultrasonic irradiationfor one minute under the conditions of 210 W and 28 kHz. The separationcondition of the polymer from the water was evaluated in the same manneras in Example 14.

The results are shown in Table 17.

After coagulating the polymer compounds according to the above-mentionedtreatment, the solid content was completely recovered in the same manneras in Example 14.

                  TABLE 17                                                        ______________________________________                                                                        Separ-                                        Sam- Unsaturated monomer        ability                                       ple  Kind                 Part      of                                        No.  A         B         C      (A/B/C) polymer                               ______________________________________                                        129*.sup.1                                                                         Polybu-   Styrene   Acrylo-                                                                              50/35/15                                                                              ◯                              tadiene             nitrile                                              130  Styrene   Acrylo-     --   71.5/28.5/0                                                                           ◯                                        nitrile                                                        131  α-Methyl-                                                                         Acrylo-     --   70/30/0 ◯                              styrene   nitrile                                                        132*.sup.1                                                                         Polybu-   Styrene   Methyl-                                                                              50/35/15                                                                              ◯                              tadiene             meth-                                                                         acrylate                                             133  Styrene   Butadiene   --   90/10/0 ◯                         ______________________________________                                         *.sup.1 Graft polymer used.                                              

We claim:
 1. An emulsifying agent for emulsion polymerization comprisingat least one member selected from the group consisting of compoundshaving the formula (II) and (III): ##STR29## ##STR30## wherein R₂represents an alkylene group having 2 to 4 carbon atoms, R₃ representsan alkylene group having 1 to 5 carbons atoms, R₄ to R₆ independentlyrepresent an alkyl group having 1 to 3 carbon atoms or --C₂ H₄ OH, nrepresents an average addition mole number of 1 to 20, and X representsan inorganic or organic anion, R₇ represents an alkyl group having 6 to20 carbon atoms, R₁₁ and R₁₂ independently represent an alkyl grouphaving 6 to 20 carbon atoms, R₁₃ represents an alkylene group having 2to 4 carbon atoms, R₁₄ represents an alkylene group having 1 to 5 carbonatoms, R₁₅, R₁₆ and R₁₇ independently represent an alkyl group having 1to 3 carbon atoms or --C₂ H₄ OH, and l is an average addition molenumber of 1 to
 30. 2. An emulsifying agent for emulsion polymerizationaccording to claim 1, wherein said emulsifying agent is a compound offormula (II).
 3. An emulsifying agent for emulsion polymerizationaccording to claim 1, wherein said emulsifying agent is a compuond offormula (III).
 4. An emulisifying agent represented by the followingformula ##STR31##